Catalytic reforming of petroleum hydrocarbons



2,996,447 CATALYTIC REFORMING F PETROLEUM HYDROCARBONS Frederick William Bertram Porter and Peter Thomas White, Sunbury-on-Thames, England, assignors to The British Petroleum Company Limited, London, England, a joint-stock corporation of Great Britain No Drawing. Filed Apr. 7, 1959, Ser. No. 804,570 Clanns priority, application Great Britain Oct. 14, 1958 7 Claims. (Cl. 208-66) This invention relates to the catalytic reforming of petroleum hydrocarbons to give products of increased octane number suitable for use in motor gasoline.

In the well-known catalytic reforming process, a naphtha fraction is contacted at elevated temperature and pressure and in the presence of hydrogen with a dehydrogenation catalyst to produce a gasoline fraction of increased octane number. Catalysts that are used commercially include molybdenum oxide on alumina and catalysts consisting essentially of platinum on alumina with or without combined halogen. A catalytic reforming process using a platinum on alumina type catalyst will hereinafter be referred to as platinum reforming and the products as platinum reformates.

The feedstock to the platinum reforming process is usually a heavy naphtha, having a boiling range for example of 90 to 175 C., and by operating underconditions to give a product having an octane number of 90 to 100 Research (clear), it is possible to achieve long catalyst life without regeneration. The volatility of the product, however, is in all cases below 45% volume recovered at 100 C. and although a product of increased volatility may be obtained by processing a feedstock with a lower final boiling point, more severe operation conditions are required with a consequent reduction in catalyst life.

The principal object of the present invention is to enable a high octane number product of increased volatility to be obtained from a heavy naphtha.

In accordance with the present invention, a heavy naphtha is subjected to platinum reforming under conditions such that regeneration of the catalyst in situ is not required (i.e. a catalyst life of at least 40 barrels of feedstock processed per lb. of catalyst), the platinum reformate is fractionated to obtain a light fraction and a heavy fraction, the heavy fraction is subjected to catalytic hydrocracking at a temperature of 900 to 1100 F., a pressure of 200 to 750 p.s.i.g., a space velocity of the liquid feedstock of 0.5 to v./v./hr and a molar hydrogen/hydrocarbon ratio of 0.5 to 15, and the liquid product of the hydrocracking operation is blended with said light fraction to give a product having an increased volatility by comparison with the platinum reformate. The preferred molar hydrogen/hydrocarbon ratio for the catalytic hydrocracking is from 4 to 10. a

The term heavy naphtha means a naphtha having an ASTM final boiling point between 150 C. and 200 C. and, preferably, an ASTM initial boiling point within the range 70 C. to 100 C.

The platinum reforming stage is preferably operated to give a reformate having an octane number Research (clear) of 90 to 100. Any convenient platinum reforming process which does not require in situ regeneration of United States Patent 2,996,447 Patented Aug. 15, 1961 "ice the catalyst may be used. The process conditions will normally fall within the following ranges:

Catalyst 0.110% platinum on alumina with or without 0.1 to 8% of halogen, particularly fluorine and/or chlorine.

Temperature 60(1)6%)%Q0 F., preferably 900- Pressure 50-1000 p.s.l., preferably 300- 700 p.s.l.

Space velocity 0.5-10 v./v./hr., preferably 1-3 v./v./hr.

Molar hydrogen/hydrocarbon ratio 0.515, preferably 6-10.

The platinum reformate is preferably fractionated so that the cut-point between the light and heavy fractions is between C. and 120 C. It has been found that the higher the cut-point, the greater is the volatility of the final blended product. The final blended product preferably has a volatility of from 40 to 60% volume recovered at 100 C. and an octane number Research (clear) of at least 90.

The present invention besides increasing the volatility of a heavy naphtha has the further advantage that it improves the octane number distribution by increasing the octane number of the lower boiling portion of the product.

Various catalysts may be used in the hydrocracking stage including known reforming catalysts, for example, platinum on alumina, with or without combined halogen, the oxides of cobalt and molybdenum (as such, or in combined form, or both) on alumina, and molybdenum oxide on alumina. The preferred compositions of the above-mentioned catalysts are as follows, all percentages being by weight of total catalyst stable at 1020 F.

0.1-10% platinum on alumina with or without 0.1-8%

ofhalogen, particularly fluorine and/or chlorine.

1.5-5% colbalt oxide and 5-25% molybdenum oxide on alumina.

525% molybdenum oxide on alumina.

The following experiments illustrate the results that may be obtained by the process according to the invention.

"EXAMPLE 1 A to 175 C. ASTM naphtha was subjected to platinum reforming to give a reformate having an octane number of 93.0 Research (clear) and a volatility of 35.5% recovered to C. The reforming conditions were: 925 F., 500 p.s.i.g., 1 v./v/hr., 10:1 hydrogen/hydrocarbon mol ratio and a catalyst of 0.7% platinum, 0.45% fluorine and0.3% chlorine, the balance being alumina. This product was fractionated into a fraction boiling below 100 C. and a fraction boiling above 100 C. The high boiling fraction was then subjected to hydrocracking at a temperature of 1000 F., a pressure of 500 p.s.i.g., a space velocity of 2 v./v./hr., and a hydrogen to hydrocarbon ratio of 5:1, using hydrogen obtained in the platinum reforming process. Separate hydrocracking operations were carried out using catalysts consisting of 0.56% platinum and 0.65% chlorine on etaalumina, 2.5% cobalt oxide and 14.9% molybdenum oxide on alumina, and 15.9% molybdenum oxide on alumina, all percentages being by weight of total catalyst stable at 1020 F. The product from the hydrocracking operation was :then blended with the fraction 31' of the platinum reformate boiling below 100 C. and the following results were obtained:

. 4 Each of the heavy platinum reformates was subjected to hydrocracking under the following conditions:

Table 1 Temperature 975 F.

Y m V 1 mm 5 Pressure 500 p.s.i.g. perfent Octane 53 Space velocity 2.0 v./v./hr. Catalyst wt t ig N Res. V ld Hydrogen/hydrocar- 5:1

It 93.! IGCOVSTQ lezgstock at 100 0. boll mol who Catalyst Cobalt and molybdenum oxides Platinum on alumina .0 .0 46.8 on alumma as 111 Example Oobalt and molybdenum o des onaluminam, gg- The treated heavy reformates were re-blended with Molybdmum Oxide mammm 6 9 their respective light reformates to give final products having the following characteristics: EXAMPLE 2 I r A 90-17s c. ASTM naphtha was subjected to re- Tables forming over a catalyst consisting of 0.56% platinum and 0.65% chlorine on eta alumina to give a yield of 70.2% wt. of a product having a Research octane (clear) Octane 3325? of 99.2 and a volatility Of 34.0% V01. recovered at 100 Cut-point onnaphtha No. Res vol. re- C. The reforming conditions were 980 F., 450 p.s.i.g., feedsmk Clear fi9 1.5 v./v./hr., and 10:1 hydrogen/hydrocarbon mol ratio. The product wasfractionated at 100 C. to give light 622 9&6 41 and heavy fractions as follows: 64. 5 96.9 46

Table 2 7 It will be seen that by increasing the cut-point from i -1 Yleld on .88 to 115 C. a 5% increase in volatility and 2.3%

ge feed to O.N. Res. Fraction (ASTM splitter, Clear increase in yield 18 obtained at the expense of a loss of DEL) f octane number of 1.7 units. Lightplatinum reformate 43-93 31. 5 74. 3 E PLE 4 Heavy platinum reiormate 111-204 68. 5 107.8 e

A 7 5-1 C. ASTM naphtha was sub ected to reform- The heavy platinum refonnate was subjected to lug over a catalyst consisting of 0.57% platinum and hydrocracking under various conditions and the prod- 35 0.81% chlorine on eta-alumina to give a yield of 71.2% uct blended with the light platinum reformate. The wt. of a product having a Research octane number (clear) following results were obtained: of 98.9 and a volatility of 42.0% recovered at 100 C.

Table 3 Blend of second stage reformate with light reformate Pressure, Temp., Space Catalyst p.s.i.g. F. Velocity, Yield on Volatility,

v./v.lhr. naphtha O .N; percent feedstock, Res. vol.

percent Clear recovered e at 100 0.

Platinum on eta-alumina 500 1, 000' 2 62.1 93,1 433 Oobaltand molybdenum oxides on gamma- 28g g alumma- 7 500 1. 000 2. 591 1 9t 3 4718 The compositions of the catalysts used were the same The product was fractionated using a cut-point of 100 as in Example 1. C. to give fractions as follows: 7

EXAMPLE 3 Table 6 A -175 C. ASTM naphtha was subjected to reforming over a catalyst consisting of 0.56% platinum and 55 B Y1 m 0.65% chlorine on eta-alumma to give a yleld of 71.6% Fraction g lfegd g Wt. of a product having a Research octane number (clear) ASTM splitter; Clear of .980 and a volatility of 34.6% v01. recovered at percentrt- C. The reforming conditions were 975 F., 450 n p.s.i.g., 1.5 v./v./hr., and 9.811 hydrogen/hydrocarbon so ggg gggfggifiggggt 3258? gig 13:; mol ratio. The product was d1v1ded into two portions which were fractionated at cut-points of 88 C. and t C. respectively. Inspection data on the fractions were The heavy Platinum reformate Was sublefited y as follows: cracking under the conditions set out in Example 3 and Table 4 i i 88 0. cut-point 7 115 C. cut-point Fraction Yield on Yield on Boiling feed to O.N. Boiling feed to O.N. c e range, 0., splitter, Res. range, 0., splitter; Res.

ASTM percent Clear ASTM percent Clear wt. t .wt.

:Light platinumreformate.-. 37-sa5 26.8 -78.2 .37-107.5 43.7 78.1 Heavy platinum reformate 104. 5-213. 5 73. 2 106. 4 130. 5 215 56. 3 w 109. 9

S the product blended with the light platinum reformate. The following results were obtained.

Table 7 Volatility, Yield percent wt. on naphtha feedstock Octane No. percent v01. Res. Clear recovered at This final product was again fractionated at a cutpoint of 100 C. and the Research octane numbers (clear) of the light and heavy fractions determined. They compared with the Research octane numbers (clear) of the light and heavy platinum reformates as follows:

Light platinum reformate, 76.0-

Light fraction of product, 82.0. Heavy platmum reformate, 1%).1

eavy fraction of product, 108.6. Thus the hydrocracking of the heavy platinum reformate has improved the octane number distribution by increasing the octane number of the fraction boiling below 100 C. We claim: 1. A process for treating a heavy naphtha to produce a product for use in motor gasoline having a volatility of from 40 to 60% volume recovered at 100 C. and an octane number Research (clear) of at least 90, comprising subjecting the naphtha to platinum reforming under conditions including a temperature within the range 6001200 'F., a pressure within the range 50 1000 p.s.i.g., a space velocity within the range 0.5-10 v./v./hr., and a molar hydrogen/hydrocarbon ratio within the range 0.5-15, such that the catalyst life is at least 40 barrels of feedstock per 1b. of catalyst, fractionating the platinum reformate with a cut-point of from 80 to 120 C. to obtain a light fraction and a heavy fraction, catalytically hydrocracking the heavy fraction at a temperature of 900-1100 F., a pressure of 200750 p.s.i.g., a space velocity of 0.5-5 v./v./hr., and a molar hydrogen/hydrocarbon ratio of from 0.5

6 -to 15, and blending the hydrocracked heavy fraction with the light fraction to give said product.

2. A process according to claim 1 wherein the molar hydrogen/hydrocarbon ratio for the catalytic hydrocracking is from 4 to 10.

3. A process according to claim 1 wherein the platinum reformate has an octane number Research (clear) of from to 100.

4. A process as claimed in claim 1 wherein the catalyst for the hydrocracking consists essentially of 0.1- 10% platinum on alumina.

5. A process as claimed in claim 1 wherein the catalyst for the hydrocracking consists essentially of 0.1- 10% wt. of platinum, and 0.1-8% Wt. of halogen on alumina.

6. A process as claimed in claim 1 wherein the catalyst for the hydrocracking comprises 1.5 to 5% Wt. of cobalt oxide and 5 to 25% Wt. of molybdenum oxide on alumina.

7. A proces as claiced in claim 1 wherein the catalyst for the hydrocracking comprises 5 to 25 wt. of molybdenum oxide on alumina.

References Cited in the file of this patent UNITED STATES PATENTS 2,361,138 Voorhies Oct. 24, 1944 2,573,829 Kassel Oct. 30, 1951 2,698,829 Haensel Ian. 4, 1955 2,731,396 Harding et a1. Jan. .14, 1956 2,758,062 Arundale et a1. Aug. 7, 1956 2,780,661 Hemminger et a1. Feb. 5, 1957 2,889,263 Hemminger et a1 June 2, 1959 UNITED :STATES- PATENT. OFFICE CERTIFICATE OF CORRECTION Patent No, 2,996,447 August 15, 1961 v Frederick William Bertram Porter et al,

It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column' 3 line 19, after "octane. insert number column 6, line 32, for "2,573,829" read 2,573,149 same column 6, line 34, for "Jan";- 14, 1956" read Jan. 17, 1956 -=-d Signed and sealed this 16th day of January 1962.

(SEAL) Attest:

ERNEST W. SWIDER DAVID L. LADD Attesting Officer Commissioner of Patents 

1. A PROCESS FOR TREATING A HEAVY NAPHTHA TO PRODUCE A PRODUCT FOR USE IN MOTOR GASOLINE HAVING A VOLATILITY OF FROM 40 TO 60% VOLUME RECOVERED AT 100*C. AND AN OCTANE NUMBER RESEARCH (CLEAR) OF AT LEAST 90, COMPRISING SUBJECTING THE NAPHTHA TO PLATINUM REFORMING UNDER CONDITIONS INCLUDING A TEMPERATURE WITHIN THE RANGE 600-1200*F., A PRESSURE WITHIN THE RANGE 501000 P.S.I.G., A SPACE VELOCITY WITHIN THE RANGE 0.5-10 V./V./HR., AND A MOLAR HYDROGEN/HYDROCARBON RATIO WITHIN THE RANGE 0.5-15, SUCH THAT THE CATALYST LIFE IS AT LEAST 40 BARRELS OF FEEDSTOCK PER LB. OF CATALYST, FRACTTIONATING THE PLATINUM REFORMATE WITH A CUT-POINT OF FROM 80 TO 120*C. TO OBTAIN A LIGHT FRACTION AND A HEAVY FRACTION, CATALYTICALLY HYDROCRACKING THE HEAVY FRACTION AT A TEMPERATURE OF 900-1100*F., A PRESSURE OF 200-750 P.S.I.G., A SPACE VELOCITY OF 0.5-5 V./V./HR., AND A MOLAR HYDROGEN/HYDROCARBON RATIO OF FROM 0.5 TO 15, AND BLENDING THE HYDROCRACKED HEAVY FRACTION WITH THE LIGHT FRACTION TO GIVE SAID PRODUCT. 